Nickel stabilizers for synthetic polymers

ABSTRACT

A new composition of nickel salts of hydroxybenzoic acids and alcohols are used as stabilizers of polymers.

United States Patent [191 Rasberger et al.

[451 Feb. 18, 1975 NICKEL STABILIZERS FOR SYNTHETIC POLYMERS [75]Inventors: Michael Rasberger, Allschwil; Jean Rody, Basel; Paul Moser,Riehen; Helmut Miiller, Binningen, all of Switzerland [73] Assignee:Ciba-Geigy Corporation, Arclsley,

[22] Filed: May 31, 1973 [21] Appl. No.: 365,801

[30] Foreign Application Priority Data June 21, 1972 Switzerland 9334/72[52] U.S. Cl ..260/45.75 N, 260/45.8 N, 260/458 NZ, 260/4585 S,260/45.9AA

[51] Int. Cl. C08f 45/62 [58] Field of Search ..260/45.75 N, 45.8 N,260/458 NZ, 45.9 R

Primary Examiner-V. P. Hoke A ttorney, Agent, or Firm Nestor W. Shust[57] ABSTRACT A new composition of nickel salts of hydroxybenzoic acidsand alcohols are used as stabilizers of polymers.

10 Claims, No Drawings NICKEL STABILIZERS FOR SYNTHETIC POLYMERS Theinvention relates to new mixtures consisting of nickel salts ofhydroxybenzoic acids and alcohols, their use for protecting polymericsubstrates and/or as dyestuff acceptors, and, as an industrial product,the polymers protected by means of these mixtures.

The mixtures consist of (A) a compound of the formula I wherein Rdenotes hydrogen or alkyl with l to 5 carbon atoms, and, of thesubstituents R and R, one denotes an alkyl radical with 3 to 8 carbonatoms and the other denotes COO, and n denotes a figure from to 2, and(B) one of the compounds a. of the formula 4 i I R\ 1T6 Bi? 8 N ca CH(010 --OH wherein R denotes hydrogen, alkyl with l to 4 carbon atoms,cycloalkyl with 5 to carbon atoms, aryl with 6 to 10 carbon atoms or aradical of the formula R denotes hydrogen, alkyl with l to 4 carbonatoms or the radical of the formula R6 R g R8 i l (on) on or R and Rtogether with the nitrogen atom denote the radical of a S-membered or6-membered saturated heterocyclic structure of the pyrrolidine,piperidine, piperazine or morpholine series, R, R and R denote hydrogen,or one of R, R and R" denotes alkyl with l to 4 carbon atoms and pdenotes 0 or 1, or

b. of the formula 9 i I R CH OH QH 0H wherein R denotes hydrogen, alkylwith l to 4 carbon atoms, OH,NH -CH OCH C(CH OH) or --CH OH and Rdenotes hydrogen, -CH OH or alkyl with 1 to 4 carbon atoms, or

c. of the formula R -enoa CH 0H wherein R denotes hydrogen, alkyl with lto 4 carbon atoms or Cl -l OR and R denoteshydrogen, alkyl with l to 18carbon atoms or phenyl, or

d. of the formula R CllCl 0 R 1 wherein R' denotes OH,

or OCH CHOHCH OH, R denotes hydrogen or alkyl with l to 4 carbon atoms,R denotes hydrogen or alkyl with 1-4 carbon atoms and q denotes 2 or 3.

e. amixture of the compounds listed under (a), (b), (c) and (d). I

Preferred mixtures are those consisting of A) a compound of the formulaI, in which R denotes hydrogen or alkyl with l to 4 carbon atoms, and,ol the substituents R and R", one denotes an alkyl radical with 3 or 4carbon atoms and the other denotes -CO()', and n denotes a value from 0to 2, especially 0.3 to 0.8, and (B), one of the compounds a. of theformula N-CH-CH- (CH P-OH wherein R denotes hydrogen, alkyl with l to 4carbon atoms, cyclohexyl, phenyl or a radical of the formula or R and Rtogether with the nitrogen atom denote the radical ofa S-membered or6-membered, saturated heterocyclic structure of the pyrrolidine,piperidine, piperazine or morpholine series, R R and R denote hydrogen,or one of R, R and R denotes methyl and P denotes 0 or 1, or

b. of the formula CH OH I wherein R denotes hydrogen, methyl, OH, NH or-CH OH and R denotes hydrogen, -CH OH or methyl, or

c. of the formula --oHoH 13 l v 15 R -(CH-.-CH2 0) R wherein R denotes-OH.

or OCH CHOHCH OH, R denotes hydrogen or methyl, R denotes hydrogen orethyl and q denotes 2 or 3.

Particularly preferred mixtures are those consisting of (A) a compoundof the formula In p Ni a) tert.Butyl no 0 coo fifPf in which n denotes avalue from 0 to 2 and (B) a compound under (a) with p equal to O, or(b), (c) or (d).

It has been found, surprisingly, that the mixtures accoQLngtQthejn entin are good stabilizers against the light-induced degradation ofsynthetic polymers, and act as dyestuff acceptors. It was already knownto stabili ze polyolefines with simple nickel benzoates. Surprisingly,the new mixtures possess a substantially better heat-stability thanthese salts. They can therefore be processed at substantially highertemperature without the polymers becoming discolored in the way thepreviously known nickel benzoates discolor the polymersf lt isfurthermore known to stabilise polyolefines bythiobisphenol-nickel-alkanolamine complexes. The new mixtures show amuch better light-protection action than these compounds.

In accordance with the definition, R, R R, R", R R R, R, R, R, R, R, Rand R can be alkyl groups.

Within the limits indicated under the formula 1, these groups can bemethyl, ethyl, n-propyl, isopropyl, nbutyl, see-butyl, tert.butyl,n-amyl, tert.amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl,n-hexadecyl or-n-octadecyl.

R and R of the component (a) mentioned under (B) can, together with thenitrogen atom, represent the radical ofa heterocyclic structure ofthcpyrrolidine series, such as, for example, pyrrolidine or 3-pyrrolidinol,of

' the piperidine series, such as, for example, piperidine,

2,6-dimethylpiperidine, 4-hydroxypiperidine and 4- methylpiperidine, ofthe piperazine series such as, for example, N-methylpiperazine,piperazine or N-Z-hydroxyethylpiperazine, or of the morpholine seriessuch as, for example, morpholinc, 2,5- and 3,S-dimethylmorpholine.

NH CH CH CH OH In the new mixtures, the molar ratio of the components Ato B is preferably 1:0.5 to I2, and according to the definition B eitherdenotes a single compound or men on on) 2 2 3 acn cu oa amen ca 0a) a non ca 0a na cu ca ou H 2 2 cu sea cu ca OH 2 2 2 VV'H2NC(CH2OH)3 ca meuca oa Ph nca cu oa 2 2 2 2 r I Nit-en ca 001! CH OH 2 2 2 2 (ea aeticupuca rnmuea ca oa 1 a a t (CH2C 0 CH5); HOCH2CHOHCH2OH Ph-N(ci-i ci1oti) z I l 0 NH 0a.. e a ocu cnouca oa (B0011 2 9 c a, con caoaca on 12d5 2 2 6 .n cu ca pa cu cn (oca en oca cuoucu oa ca oa I H' B0011 e ca ocu oa The new mixtures provide protection against degradation forsynthetic polymers, preferably oz-olefine polymers. such aspolypropylene, optionally crosslinked polyethylene, polyisobutylene,polymethylbutene-l, polymethylpentene-l, polybutene-l, polyisoprene andpolybutadiene; polystyrene and its copolymers such as. for example,polyacrylonitrile-styrene copolymers orpolyacrylonitrile-butadiene-styrene copolymers; copolymers of themonomers on which the homopolymers mentioned are based, such asethylenepropylene copolymers, propylene-butene-lcopolymers andterpolymers of ethylene and propylene with a diene such as, for example,hexadiene, dicyclopentadiene or ethylidenenorborncne; mixtures of theabovcmentioned homopolymcrs such as, for example mixtures ofpolypropylene and polyethylene. polypropylene and polybutene-l.polypropylene and polyisobutylene. Polypropylene and its mixtures andthe copolymers which contain polypropylene units are preferred.

4 V I @nucu ca oa 4 T h I a mixture of such compounds. In the lattercase, the molar ratio A to B is the ratio of the mols of the compound Ato the sum of the mols of the compounds under B.

The new mixtures are incorporated into the substrates in a concentrationof 0.01 to 5% by weight, calculated relative to the material to bestabilized. Preferably, 0.05 to 1.5, and particularly preferably 0.1 to0.8, by weight of the mixtures, calculated relative to the material tobe stabilized, are incorporated into the latter.

The incorporation can be effected after the polymerisation, for exampleby mixing the mixtures and, optionally. further additives into the meltin accordance with the methods customary in the art. before or duringshaping. or by application of the dissolved or dispersed mixtures to thepolymer, optionally with subsequent evaporation of the solvent.

The mixtures of the components A and B can also be incorporated in theform of a masterbatch, which contains these mixtures, for example, in aconcentration of 2.5 to 25% by weight, into the polymers to bestabilised. 1n the case of crosslinked polyethylene, the mixtures areadded before crosslinking. As further additives together with which thestabilizers usable according to the invention can be employed, theremaybe mentioned:

1. Antioxidants of the aminoaryl and hydroxyaryl series. Amongst thelatter, there should be mentioned the sterically hindered phenolcompounds, for example: 2,2'-thiobis-(4-methyl-6-tert.butylphenol), 4,4-thiobis-(3-methy1-6-tert.butylphenol),2,2'-methylenebis-(4-methyl-6-tert.butylphenol), 2,2'-methylene-bis-(4-ethyl-6-tert.butylphenol), 4,4 '-methylene-bis-( 2-methyl-6-tert.butylphenol), 4,4-butylidene-bis-(3-methyl-6-tert.butylphenol), 2,2'-methylene-bis-[4-methyl-6-(a-methylcyclohexyl)-phenol], 2,6-di(2-hydroxy-3-tert.butyl-5-methylbenzyl)-4-methylphenol,2,6-di-tert.butyl-4-methylphenol, 1,1,3-tris-2-methyl-(4-hydroxy-5-tert-butyl-pheny1)-butane, 1,3,5-trimethyl-2,4,6-tri-(3,S-di-tert.butyl-4-hydroxybenzyl)-benzene, estersof B-4-hydroxy-3,5-di-tertbutylphenyl-propionic acid with monohydric orpolyhydric alcohols, such as methanol, ethanol, octadecan01, hexanediol,nonanediol, thiodiethylene glycol, trimethylolethane or pentaerythritol,2,4-bisoetylmercapto-6-(4-hydroxy-3,5-di-tert.butylanilino)- s-triazine,2,4-bis-(4-hydroxy-3,5-di-tert.-butylphenoxy)-6-octylmercapto-s-triazine, l,l-bis-( 4-hydroxy-2-methyl)-5-tert.-butylphenyl)-3-dodecylmercaptobutane,4-hydroxy-3,5-di-tert.-butylbenzylphosphoric acid esters, such as thedimethyl, diethyl or dioctadecyl ester,(3-methyl-4-hydroxy5-tert.-butylbenzyl)-malonic acid dioctadecyl ester,S-(3,5- dimethyl-4-hydroxyphenyl)-thioglycollic acid octadecyl ester,and esters of bis-(3,5-di-tert.-butyl-4- hydroxybenzyl)-malonic acid,such as the didodecyl ester. the dioctadecyl ester and the2-dodecylmereaptoethyl ester.

2. UV-absorbers and light protection agents, such as:

2-(2'-hydroxyphenyl)-benztriazoles, for example the -methyl-,3,5'-di-tert.butyl-, 5'-tert.butyl-, 5- chloro-, 3,5-di-tert.butyl-,5-chloro-3'-tert.butyl- 5'-methyl-, 3',5'-di-tert.amyl, 3'-methyl-5'-B-carbomethoxyethyland 5-chloro-3',5-ditert.amyl derivative.

b. 2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines. for

example the 6-ethylor 6-undec \'l-derivative.

c. 2-Hydroxy-benzophenones. for example the -1- hydroxy-,4-methoxy-,4-octoxy-. -l-decylox v-, 4- dodecyloxy-, 4,2,4-tri-hydroxy or2'-hydroxy--l,-ldimethoxy derivative.

d, l,3-Bis-(2-hydroxy-benzoyl)-benzenes, for example 1,3-bis-( 2-hydroxy-4-hexyloxy-benzoyl benzene,1,3-bis-(2-hydroxy-4'-oetoxy-bcnzoyl)- benzene andl,3-bis-(2-hydroxy-4-dodecyloxybenzoyl)-benzene.

e. Aryl esters of optionally substituted benzoie acids, such as, forexample, phenyl salicylate, octylphenyl salicylate, benzoylresorcinol,dibenzoyl-rcsorcinol. and 3,5-di-tert.butyl-4-hydroxybenzoic acid2,4-ditert.butylphenyl ester or octadeeyl ester.

f. Acrylates, for example a-cyano-B,,B-

diphenylaerylic acid ethyl ester or isooctyl ester.oz-carbomethoxycinnamic acid methyl ester,a-eyano-B-methyl-p-methoxycinnamic acid methyl ester or butyl ester andN(B- carhomethoxy-vinyl)-2- methyl-indoline.

g. Oxalic acid diamides, for example 4,4-dioctyloxyoxanilide,2,2'-di-octyloxy-5,5-di-tert.butyl-oxanilide and2,2'-di-dodecyloxy-5,5-di-tert- .butyl-oxanilide.

3. Nucleating agents, such as 4-tert.butylbenzoic acid, adipic acid anddiphenylacetic acid.

4. Compounds which destroy peroxide, such as esters of B-thiodipropionicacid, for example the lauryl, stearyl, myristyl or tridecyl ester. Saltsof 2- mercaptobenzimidazole, for example the zinc salt, anddiphenylthiourea.

5. Other additives such as plastieisers, antistatic agents, dyeingauxiliaries, flameproofing agents, pigments, carbon black, asbestos,glass fibres, kaolin, talc and blowing agents.

6. Co-stabilizers, such as salts of alkaline earth metals, preferablysalts of alkaline earth metals and carboxylie acids, such as, forexample, calcium stearate, calcium palmitate, calcium oleate and calciumlaurate.

The manufacture of the compound of the formula l is described in U.S.Pat. No. 3,189,690.

The invention is described in more detail in the examples which follow.Therein, parts denote parts by weight and percentages denote percentagesby weight.

EXAMPLE I 1,000 parts of polypropylene powder [melt index 1.5 g/lOminutes (230C, 2,160 g)] are mixed in a drum mixer with 0.5 part oftetrakis-B(3,5-di-tert.-butyl-4- hydroxyphenyl)-propionic acidpentaerythritol ester, 3 parts of dilauryl thiodipropionate (DLTDP), 5parts of Ni 3,5-di-tert,butyl-4-hydroxy-benzoate which contains 2.36% ofwater bound as a complex, and an additive of the table which follows,and the whole is subsequently homogenized for 10 minutes at 200C in aBrabender plastograph. The polymer mass is then pressed in a heatedpress for 6 minutes at 240C to give 1 mm thick sheets. A visualassessment of the test specimens for their discoloration gives thefollowing results:

w 9 10 A 0 Parts Additive Appearance of the Sheet after 6 minutes at240C none grey discoloration l 2 parts N(CH CH 0H) no discoloration 2 15 Parts NH(CH CH 0H) no discoloration 3 1 part NH UJH CH OH) slight greytinge 4 1.5 parts (CH NCH CH CH OH no discoloration 5 2 parts C H N(OHCH OH) no discoloration 6 2 parts l l(CH CI-iOHCH slight grey tinge 7 2parts Ph-N(CH CH OH) no discoloration 8 1 part HOCH CHOHCH 0H no discolora'tion- EH 0 9 1 .5 parts HOCH -(IJ-CH OH no discoloration CH OH 102.5 parts C H 0CH OHOHCH 0H no discoloration 11 1 .5 parts HN NCH CH OHno discoloration 12 2.5 parts cn cn wcn cn ocn cnoncnon no discolorationEXAMPLE 2 stretched at an elevated temperature using a stretch ratio of1:6 and are wound up (gauge of the tapes: 700900 den; tensile strength:5.5-6.5 g/den).

teetive action of the individual light protection agents. The valuesobtained are listed in the table WlllL'll lollows:

No. Parts Additive Hours of Exposure until 50% tensile strength isreached none 3, 5

1 2 parts N(CH CH 0H) 3,750

2 1 .5 Parts I-ZH(CH CH 0H) 3,700

3 1 part NH (CH CH 0H) 3,800

4 1.5 Parts (CH NCH CH CH OH 3,600

5 2 parts 0 H N(CH CH OH) 3,650

6 2 parts N(CH CHOHCH )5 5,700

7 '2 parts Ph--N(CH CH OH) 3,600

8 1 part HOCH CHOHCH OH 3,650

(IIH OH 9 1 5 parts HOCH -C-CH OH 3,800

CH OH 10 2.5 parts C H 0CH CH0HCH 0H 5,950

11 1 .5 parts an 110a on on 3,550

12 2.5 parts CH CH (0CH CH 0CH 0H0HOH 0H 3,850

13 1 part (CH NCH CHOHCH 3,75

14 2 parts 0 1 1 OCH GHOHCH OH 3,900

What we claim is:

l. A composition of matter stabilized against therwherein:

R denotes hydrogen or alkyl with l to 5 carbon atoms,

of the substitucnts R and R", one denotes an alkyl with 3 to 8 carbonatoms and the other denotes COO', and n denotes a value of 0 to 2,

B. an alkanolamine of the formula .N- H-CH- CH OI-I 5 R denoteshydrogen, alkyl with l to 4 carbon atoms, cycloalkyl with 5 to 10 carbonatoms, aryl with 6 to 10 carbon atoms or a radical of the formula R6 RR8 l l l -cH-cH-(cH) R denotes hydrogen, alkyl with l to 4 carbon atomsor the radical of the formula t l -GH-CH(CH)p-OH or R and R togetherwith the nitrogen atom denote the radical of a 5-membered or 6-memberedsaturated hctcrocyclic structure of the pyrrolidine, piperidine orpiperazine series,

R, R and R denote hydrogen or one of R, R and R denotes alkyl with l to4 carbon atoms, and

p denotes or 1,

such that the amount of components (A) and (B) is in the concentrationof 0.01 to by weight of the total composition and the molar ratio of A:Bis in the range of 1:05 to 1:2,

C. from 0.05 to 0.1% by weight of the total composition of a hinderedphenol antioxidant selected from the group consisting oftetrakis-,B(3,5-di-tert-butyl- 4-hydroxyphenyl)-propionic acidpentaerythritol ester and B-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid octadecyl ester, and

D. from 0 to 0.3% by weight of the total composition of an ester ofB-thiodipropionic acid selected from the group consisting of dilaurylthiodipropionate and distearyl thiodipropionate.

2. A composition according to claim 1 where the alkanolaminc (B) is ofthe formula wherein:

R denotes hydrogen, alkyl with l to 4 carbon atoms,

cyclohexyl, phenyl or a radical of the formula R6 R7 R8 l I --CH--CH(CH-OH nickel benzoate (A) is wherein:

n denotes a value of 0 to 2, and where the alkanolamine (B) is of theformula wherein:

R denotes hydrogen, alkyl with l to 4 carbon atoms,

cyclohexyl, phenyl or a radical of the formula -CHCH--OH R denoteshydrogen, alkyl with l to 4 carbon atoms or a radical of the formula orR and R together with the nitrogen atom denote the radical of asaturated hctcrocyclic structure of the pyrrolidine, piperazine series,and

R and R denote hydrogen or one of R and R denotes methyl.

4. A composition according to claim 1 where the amount ofcomponents (A)and (B) is in the concentration of 0.05 to 1.5% by weight ofthe totalcomposition.

5. A composition according to claim 1 where the amount ofcomponents (A)and (B) is in the concentration of 0.1 to 0.8% by weight of the totalcomposition.

6. A composition according to claim 1 where the polymonoolefin ispolypropylene.

7. A composition of claim 3 where n is 0.75.

8. A composition of claim 24 where the alkanolamine (B) is 9. Acomposition of claim 3 where the alkanolamine (B) is an cn cn tn 10. Acomposition of claim 3 where the alkanolamine (B) is

1. A COMPOSITION OF MATTER STABLISED AGAINST THERNAL AND LIGHTDEGRADATION AND DISCOLORATION WHICH COMPRISES A POLYMONOOLEFIN AND AMIXTURE OF A. A NICKEL BENZOATE OF THE FORMULA
 2. A compositionaccording to claim 1 where the alkanolamine (B) is of the formula
 3. Acomposition according to claim 1 where the nickel benzoate (A) is
 4. Acomposition according to claim 1 where the amount of components (A) and(B) is in the concentration of 0.05 to 1.5% by weight of the totalcomposition.
 5. A composition according to claim 1 where the amount ofcomponents (A) and (B) is in the concentration of 0.1 to 0.8% by weightof the total composition.
 6. A composition according to claim 1 wherethe polymonoolefin is polypropylene.
 7. A composition of claim 3 where nis 0.75.
 8. A composition of claim 24 where the alkanolamine (B) isN(CH2CH2OH)3.
 9. A composition of claim 3 where the alkanolamine (B) is10. A composition of claim 3 where the alkanolamine (B) isC6H5N(CH2CH2OH)2.